CA1164339A

CA1164339A - Fungicidal compositions containing benzenamines and fungicidal methods

Info

Publication number: CA1164339A
Application number: CA000368024A
Authority: CA
Inventors: Albert J. Clinton, (Deceased)
Original assignee: Eli Lilly and Co
Current assignee: Eli Lilly and Co
Priority date: 1980-01-08
Filing date: 1981-01-07
Publication date: 1984-03-27
Also published as: FI810025L; KR830005104A; PT72315A; GR72310B; PH16393A; CS221812B2; PT72315B; KR840001232B1; US4304791A; PL229119A1; DD157292A5; HU187757B; EG14795A; PL124733B1

Abstract

Abstract of the Disclosure Compositions useful in the treatment of fungal infec-tions in soil and on plants are described. They comprise a compound of the formula and a suitable carrier, diluent or excipient therefor.
Methods for the treatment of plant and soil fungal infec-tions with the above compositions are also described.

Description

1 ~ 6~339 Funqicidal compositions containinq benzenamines and fun~cidal methods Benzenamines have experienced widespread usage in the field of agriculture. Numerous benzenamines are known which are effective as herbicidal agents. Among the most widely used herbicidal benzenamines are trifluralin, which is N,N~di~n-propyl-2r6-dinitro-4-trifluoromethylbenzen-amine, butralin, which is N-(l-methylpropyl)-2,6-dinitro-4-tert.-butylbenzenamine, and benefin9 N~butyl-N-ethyl-2,6-dinitro-4-trifluoromethylbenzenamine.
Several benzenamines are known to be useful in animal health. For example, European Patent No. 156, published January 10, 1979, discloses various N-(2,4-~dinitro-6-trifluoromethylphenyl)ben~enamines which are said to exhibit useful insecticidal, acaricidal, nemato-cidal, ins~ct growth retardantr fungicidal and bacteri idal activity. Similarly, antifungal benzenamines are disclosed in U.S~ Patent No. 4 ,152, 460 .
This invention is concerned with certain N-(nitro-phenyl)-polyfluoroethoxybenzenamines which are potent antifungal agents, and which also display ectoparasitic activityO The compounds are described in copending Canadian application Serial NoO 368,0~3.
This invention concerns novel formulations contain-ing such compounds, and a method for treating soil and plant fungal diseases. The invention is more particularly directed to compositions for the treatment of fungal infec-tions in soil and on plantsl comprising N-(nitrophenyl)-(tetra and penta fluoroethoxy)benzenamine compounds of the formula ~ 3 ~339 R4 ~ R1 ~ ~ 3 R5 ~ o-t ~

I

wherein:
RO is hydrogen or fluoro Rl is hydrogen or Cl-C2 alkyl;
R2 and R3 independently are hydrogen or halo;
R4 is hydrogen, trifluoromethyl, cyano, C1 C~
alkyl, hydroxycarbonyl or Cl~C~ alkoxycarbonyl;
R is hydrogen, halo, nitro, hydroxy, methoxy or amino;
R6 is hydrogen or nitro; and the physiologically-acceptable salts thereof, together with a suitable carrier, diluent or excipient.
Preferred compounds useful in this invention include those having the above formula wherein R6 is nitro.
Especially preferred compounds useful in this invention are those of the formula ,CF3 ~ 3 "~=r=~<
~~~ --N-~
~s/ ~O OCF2CF2R

II

~.~"~

~ 3 ~

X-4836-1 -3~

wherein:
R0 is hydrogen or fluoroi R1 is ~ydrogen or C~-C2 alkyl;
R and R3 indep~ndently are hydrogen or S halo;
R is hydrogen or halo; and the physiologically-acceptable salts thereof.
Additionally preferred compounds are those wherein R~ and R3 are the same, R4 is hydrogen, tri-fluoromethyl, cyano, Cl-C4 alkyl, or hydroxycarbonyl;
R5 is chloro, bromo or ni~ro; and R6 i~ nitro.
Anoth2r preferred group of benzenamines according to this in~ention have the above formula h i R~ Rl R2 R3 and R5 all are hydrogen, R is trirluoromethyl and R is nitro.
A further embodiment of this invention is formulation comprising an N-(nitrophenyl)-polyfluoroethoxy-benzenamine defined by the above general formula aamix~d with a suitable carrier, diluent or excipient therefor.
Also provided by this inventlon is a method for treating fungicidal infection.s in plants and in soi.l comprising applying to the locus to be trea-ted an antifungal amount of a ben~enamin~ dexined by the above formula.
~ n the above formula detines hydrogen or Cl-C2 alkyl, namely methyl or ethyl.
R2, R3 and R5 include th~ groups re.ferred to herein as "halo". The term bears its ar~-recognize-fl meaning of fluoro, chloro, bromo and iodo. Preferred halo qroups defined by R2, R3 ~nd R5 ar~ chlo.-o ~n,~
bromo.

~ 3 ~ 3~

X-4836-1 ~4~

R4 in the above formula includes Cl-C~ alkyl gro~lps, which are straight and branched chain alkyl group ha~ing from one to four carbon atoms. Typical Cl-C4 alkyl groups include methyl, ethyl, n-propyl iso-propyl, n-butyl and tert~-butyl.
-- 4~
R additionally defines a C1-C4 aikox~car-bonyl moiety, for instance metho~ycarbonyl, ethoxy-carbonyl, isopropoxycarbonyl, n-butoxycarbonyl, and related groups.
The N-nitrophenyl-(tetra and penta)~luoro-ethoxyben~enamines comprehended by this invention can be prepared by any of se~eral chemical processes. A
preferred and commonly utilized process involves the condensation reaction of a substituted phenyl electro-lS philic agent with a phenylamine derivative. For example, a polyfluoroethoxyphenyl electrophilic agent such as a phenyl halide can be condensed with a nitro-phenylamine according to the following scheme:
Rs NO2 Rl R2 R3 R4 NO2 R' ~ 3

2 0 ~ NH ~ X-~ /R

CF2CF2R ~a ~CF2CF2R

O Rl R2 R3 R4 R5 and R6 are as defined above, and X ls a good leaving group such as halo, for instance chloro, bromo or iodo. A similax, yet alter-native, process comprises _ondensing a nitrophellyl electrophilic agent with a polyfluoroetho~yphenvlamine according to the following scheme:

~ ~ 6~3~9 ~-4~36-1 5~

R~ N 02 R~ R2 R4 N 02 R1 R 3 $=~X~ ,~
~ ~9-X + NH~ J --~ -N-~
R ~ CF~.CF~R R ~6 1CF2CF~R

h i R0 Rl R2 R3 P4, R5 and R6 are as defined above, and X is a good leaving group such as halo.
Such reactions are preferably carried ou~ when Rl is hydrogenO
According to the processes outlined above, a substituted phenyl electrophilic agent such as a tetra or pentafluoroethoxyphenyl chloride is mixed with about an equimolar quantity of a nitrophenylamine. The condensation reaction generally is carrled out in an unreactive organic solvent and in the presence of a strong base. Commonly used unreactive organic solvents include amides, for instance dimethylformam.ide or hexamethylphosphortriamide; ethers such as tetrahydro-furan, diethyl ether, or dioxane; sul~oxides such asdimethyl sulfoxide; alcohols such as methanol or ethanol; and related solvents. Strong bases which may be utilized in the reaction include alkali metal hydrides, for instance sodium hydride or lithium hydride; amines such as triethylamine, pyridine, Ds~
(1,5-diazabicyclo [4~3.0]-non-5-ene) and DBU (1,5-diazabicyclo-[5.4.0] undec-5-ene, carbonates such as potassium carbonate and sodium carbonate; alkoxides such as potassium tert.-butoxide, and the liXe.

1 3 ~33~

~-4836-l -6-The condensation reaction generally is carried out by first a~ding a phenylamine to a strong base in a suitable solvent. ~or instance, a phenyl-amine such as 3-(1,1,2,2-tetrafluoroethoxyphenyl)amine can be reacted with a base such as sodium hydride in a solvent such as dimethylformamide. The reactants can be emplo~ed in about equimolar quantites, or if desired an excess of base, for example about a 0.1 to about a 10 molar excess, can be utilized if desired. The phenylamine and the strong base generally are allowed to react for up to about 3 hours at a temperature of about -30 to about 30C., preferably about 0 to about 25C. Following the initial reaction of the phenylamine and the strong base, the desired substituted phenyl electrophilic agent, for instance a compound such as 2,4-dinitro~6-trifluoromethylphenyl chloxide, is added to the reaction mixture, and the reaction is permited to continue for about 2 to about 48 hours at a tem-perature of about 0 to about 100C.
The product of the condensation reaction is a compound comprehended by this invention and i5 readily isolated by simply adding the reaction mixture to an aqueous acid solution, for instance dilute aqueous hydrochloric acid or sulfuric acid. The desired product often precipitates out of the aqueous acid solution as a solid or an oil. ~lternatively, the product ma~ be e~tracted into a water immiscible organic solvent such as diethyl ether, ethyl acetate, dichloromethane, or t~e like. Removal of the organic solvent, for instance by e~aporation under reduced X-4836-1 ~7-pressure, then provides a compound of this invention.
The product thus formed can be further purified if desired by any of several standard methods, including column chromatography over a solid support such as silica ~el or the like, or cr~stallization from commGn sol~ents such as ethanol, benzene, skelly B, diethyl ether, acetone, and the like.
Certain benzenamines provided by this invention can be prepared by modification of an existing benzenamine prepared as described above. For example, N-alkylation of a benzenamine having the above formula wherein R1 is hydrogen affords the corresponding benzenamine wherein Rl is Cl-C2 alkyl. Such alkylation reactions typically are accomplished by combinlng an alkylating agent with a benzenamine (wherein Rl is hydrogen) in an unreactive organic solvent and in the presence of a base. Typical alkylating agents commonly used include alkyl halides such as methyl bromide or ethyl iodide, as well as sulfates such as dimethyl sulfate and diethyl sulfate.
Commonly used solvents include acetone, benzene, methyl ethyl ketonet dimethylsulfoxide and the like. The alkylation routinely is substantially complete within about two to about seventy-two hours when carried out at a temperature of about 30 to about 150C. The M-alkylated benzenamine is qenerally isolated by extraction of the reaction mixture wi~h A solven~ such as diethyl ether or benzene, and then evaporation of the solvent from the extract. The product can be further purified if desired by crystallization, chroma-tography, distillation, or related purification techniques.

3 3 ~

X-4836-l -8-Benzenamines bearin~ a carboxylic acid moiety, that is to say compounds of the above general formula wherein R4 is hydroxycarbonyl, are readily esterified to provide benzenamines wherein R4 is a S Cl-C4 alkoxy carbonyl group. Such conversion can be accomplished by standard esterification reactions.
Methyl esters are often preferably prepared by simply reacting a free acid with diazomethane in a suitable solvent such as diethyl ether. Esterification can also be accomplished by condensing a benzenamine carboxylic acid with a Cl-C4 al~anol in the presence of an acid, for instance sulfuric acid or the like. Alternativelv, a benzenamine carboxylic acid can be con~erted to an acid halide, and the acid halide then can be condensed with a Cl-C4 alkanol. For example, reaction of a benzenamine ~uch as N-(2-nitro-4-hydroxycarbonyl-phenyl~-4-(1,1,2,2-tetra~luoroethoxy)benzenamine with oxalyl chloride affords N-(2-nitro-4-chlorocarbonyl-phenyl)-4-(1,1,~,2-tetrafluoroethoxy)benzenamine, which when reacted with an alkanol such as isopropanol af~ords N-.~2-nitro-4-isopropoxycarbonylphenyl)-4-(1,1,2,2-tetrafluoroethoxy~benzenamine.
Benzenamines having the above formula wherein one or both of R2 and R3 are hydrogen can be halogenated by reaction with a halogenating agent in a suitable solvent. For instance, a compound such as N-(2,6-dinitro-~-trifluoromethyl)-3-(1,1,2,2-tetra~luoro-ethoxy~benzenamine can be reacted with about one equivalent, or an excess if desired, of bromine in the presence of a solvent such as dichloro~ethane or a 3 ~

X-~836-1 ~9~

mixture of acetic acid and water. Such reaction effects bromination to provide, for instance. ~-(2,6-dinitro-4-trifluoromethyl)-2,4-dibromG S-(1,1,2,2-tetrafluoroethoxy)benzenamine.
When ~esired, the above described halogenation reaction can be carried out utilizing less than one molar quantity of halogenating agent, thereby effecting monohalogenation instead of dihalogenation. The mono-halogenation product can be further halogenated if desired with the same or a different halogenating agent. For instance a benzenamine such as N-(2,6-dinitro-

4-trifluoromethylphenyl)-3-(1,1,2~2,2-pentafluoro-ethoxy)benzenamine can be reacted with about a 0.5 molar amount of chlorine in dichloromethane at about 25C. to give ~-(2,6-dinitro-~-trifluoromethylphenyl)-2-chloro-3-(1,1,2,2,2-penta~luoroethoxy)ben2enamine.
The latter compound can be further halogenated, for instance by reaction with about a 0.5 to 10. molar amount of bromine in dichloromethane, to provide the corresponding dihalogenated derivative, for example N-(2,6-dinitro-4-trifluoromethylphenyl)-2-chloro-~-bromo-5-~1,1,2,2,2-pentafluGroethoxy)~enzenamine.
The benzenamines contemplated herein wherein R1 ls hydrogen are weakly acidic in nature by virtue of the acti~ated proton attached to the amino nitrogen atom to which the two aromatic rings are attached.
Because of this acidic nature, the ben~enamines readily form physiologically-acceptable salts by reaction with any of a number of common inorganic and organic bases. The salts are in general solids 3 ~ 9 ~-4~36-1 -10~

and thus lend themselves to purification by crys-talllzation from common solvents such as ethanol, acetone, ethyl acetate, methyl ethyl ketone, and the like.
The salts provided herein are prepared by reaction of about equimolar quantiti~s o~ a benzenamine and a ~ase. Inorganic bases commonly employed to form salts of this i~vention include the alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, as well as alkali metal amides such as lithium amide and potassium amide. Routinely used organic bases include alkali metal alkoxides such as potassium tert.-butoxide and sodium methoxide, as well as alkali metal amides such as lithium or potassium diisopropylamide.
When it is desired to regenera-te the lree amine from an addition salt, the salt is simply reacted with an acid such as hydrochloric acid or sulfuric acid. For example, reaction of the sodium salt of N-(2,4-dinitrophenyl)-3-(1,1,2,2-tetrafluoroethoxy)-benzenamine with about one equivalent amount of hydro-chloric acid converts the salt to a free amin~ to provide N (2,4-dinitrophenyl)-3-(1,1,2,2-tetrafluoro-ethoxy~benzenamine.
Representative benzenamines comprehended by this invention include the following:
N-(2,6-dinitro-4-trifluoromethylphenyl)-3-(1,1,2,2-tetrafluoroethoxy~benzenamine.
N-(2,6-dinitro-4-cyanophenyl)-2-(1,1,2,2-tetrafluoroethoxy)benzenamine;

3 3 ~

X-~836 1 N-(2,4 dinitro-6 trifluoromethylphenyl)-N-ethyl-4 (1,1,2,2-tetrafluoroethoxy~benzenamine;
N-(2,4-dinitro-6-hydroxycarbonylphenyl)-3-(1,1,2,2-tetrafluoroethoxy)-4-chlorobenzenamine;
5N-(3-nitro-4-chlorophenyl)-N-methyl-4-(1,1,2,2-tetrafluoroethoxy)benzenamine;
N-(2-trifluoromethyl-4-nitrophenyl)-2-(1,1,2,2-tetrafluoroethoxy)benzenamine;
N-(3-trifluoromethyl-4-nitrophenyl)-N-10methyl-3-(1,1,2,2-tetrafluoroethoxy)benzenamine;
N-(2,6-dinitro-4-ethoxycarbonylphenyl)-3-(1,1,2,2-tetrafluoroethoxy)-4,5-dichlorobenzenamine;
N-(2-nitrophenyl)-3-(1,1,2,2-tetrafluoro-ethoxy)benzenamine;
15N-(2,4-dinitro-6-isopropyl)-N-ethyl-2,6-dichloro-4-(1,1,2,2-tetrafluoroethoxy)benzenamine;
N-(2,4,6-trinitrophenyl) N-ethyl-3-(1,1,2,2-tetrafluoroethoxy)benzenamine;
N-~2,6-dinitro-3-bromo-4-trifluoromethyl-20phenyl~-4-(1,1,2,2,2-penta~luoroethoxy)benzenamine;
N-(2-nitro-4-tert.-butylphenyl)-2,6-dibromo-4-(1,1,2,2-tetrafluoroethoxy)benzenamine;
N-(3,4-dinitrophenyl)-2-bromo~6-chloro-4-(1,1,2,2,2-pentafluoroethoxy)benzenarnine;
25N-(2,3,4-trinitro-5-methylphenyl)-2-(1,1,2,2-tetrafluoroethoxy)-3,5-dibromobenzenamine;
N-~2-nitro-4-ethoxycarbonylphenyl~-N-ethyl-3--~1,1,2,2-tetrafluoroethoxy)bellzenamine;
N-(2,4~dinitro-6-_-butylphenyl)-2,6-30dichloro-3-(1,1,2~2-tetrafluoroethoxy)benzenamine;

N-(2,6-dinitro-4-hydroxycarbonylphenyl)-3-(1,1,2,2-tetrafluoroethoxy)benzenamine;
N-(2,4~dinitro-6-hydroxycarbonylphenyl)-2,6-difluoro-4-(1,1,2,2-tetrafluoro)benzenamine;
N-(2,4,6-trinltrophenyl)-N-methyl 2,4-diiodo-5-(1,1,2,2-pentafluoroethoxy)benzenamine, Sodium N-(2-nitrophenyl)-3-(1,1,2,2,2-pentafluoroethoxy)ben~enamide;
Potassium N-(2,6-dinitro-4-cyanophenyl)-2,6-dibromo-3-(1,1,2,2-tetrafluoroethoxy~benzen-amide;
Lithium N-(2,4-dinitro-6~trifluoromethyl-phenyl)-3-(1,1,2,2-tetrafluoroethoxy)benzenamide;
Sodium N-(2,6-dinitro-4-trifluoromethyl-phenyl)-4-(1,1,2,2-tetrafluoroethoxy)benzenamide;
Lithium N-(2,4,6-trinitrophenyl)-2-(1,1~2,2-tetrafluoroethoxy)benzenamide;
~-(2-trifluoromethyl-5-chloro-4,6-dinitro-phenyl)-4-(1,1~2,2-tetrafluoroetlloxy)benzenamine;
N-(2,4-dinitro-6-hydroxycarbonylphenyl~-2,4-dibromo-5-l1,1,2,2-tetrafluoroethoxy)ben2enamlne;
Potassium N-~2,6-dinitro-4 trifluoro-methyl~-3-bromo-4-(1,1,2,2-tetrafluoroethoxy)benzen-amide;
Sodium N ~2-nitro 3-chloro-4-cyanophenylj 2-(1,1,2~2-tetrafluoroethoxy)benzenamide;
N-t2,6-dinitro-~-trifluoromethylphenyl)-2,4-dichloro-5-(1,1,2,2,2-pentafluoroethoxy)benzen-amine;
N-(2,4,6-trinitrophenyl)-3-(1,1,2,2,2-pentafluoroethoxy~benzenamine;

J 3 ~ A 3 3 9 X-4836-l -13-N-(2-trifluoro~ethyl-~-nitrophenylj-3-(1,1,2,2,2-pentafluoroethoxy)ben2enamine;
N-(2,4 dinitro~6-tr~fluoromethylphenyl)-~-ethyl-4-(i r 1~2~2~2-pentar-luoroethoy~y)be~zenamine;
and the like.
The detailed examp~es which follow illustrate the preparation of representative compounds embraced by the present invention. The examples are representative only and should not be construed as limiting in any respect.
_ample 1 N-(2,4-dinitro-6 trifluoromethylphen~l)-4 (1,1,2,2-tetrafluoroetho~y)berzenamine.
To a stirred solution of l.0 g. of 4-(1,1,2,2-tetrafluoroethoxy)phenylamine in 50 ml. of ethanol containing 3.0 ml. of triethylamine were a~ded in one portion 1.3 g. of 2,4-dinitxo-5-trifiuoromethyl-phenyl cnloride. The reaction mixture was heated at ~o reflux for sixteen hours following the addit~on. The reaction miY~tuxe thsn was added to lO0 ml. o~ ice water containing about lO ml. of hydrochloric acid. The precipitate which ormed was collected and dissolved in diethyl ether. The ethereal solution was washed with water and dried, and the solvent was removed by evap-oration under reduced pressure to provide 1O2 ~O of N-(2,4-dinitro-6-tri~luoromethylp~ienyl)-4-(1,1,2,2-tetrafluoroethoxy)~enzenamine.
~ield 54.9% M.P. 105-107C.

~ J ~ ~39 ~-4836-1 -14-Analysis calculated for C15H8F7N3O5 Theory: C, 40.65; H, 1.82; N, 9c48, Found: C, 40.89; H, 2.08; N, 9.66 Example 2 ~ -(2,6-dinitro-4-tert.-butylphenyl)-4-(1,1,2,2~tetrafluoroethoxy)benzenamine.
A solution of 2.5 g. of 4-(1,1,2,2-tetra~
fluoroethoxy)phenylamine hydrochloride in 30 ml. of ethanol containing 5.0 ml. of triethylamine and 2.~ g.
of 2,6-dinitro-4-tert.-butylphenyl chloride was stirred and heated at reflux for sixteen hours. The reaction mixture was then slowly added to 100 ml. of ice water containing 10 ml. of concentrated hydrochloric acid, 1~ and the aqueous mixture was stirred for thirty -minutes. The oil which ormed was collected and crystallized from skelly-B solvent and diethyl ether to give 2.4 g. of N-(2,6-dinitro-4-tert.-butylphenyl)-4-(1,1,2,2-tetrafluoroethoxy)benzenamine.
Yield 51.3~ MoP~ 142-143C.
Analysis calculated for C18H17F4N3O5 Theory: C, 50.12; H, 3.97; N, 9.74.
Found: C, 50.28; ~, 4.02; N, 9.99.
Examples 3-12 Following the general procedure of Examples 1 and 2, the appropria~e fluoroethoxyphenylamine was reacted with the appropriate nitrophenyl halide in the presence of triethylamine in ethanol to give the following benzenamines.

~ ~ ~41339 N-(2,6-dinitro-4~cyanophenyl)-4-(1,1,2,2-tetrafluoroethoxy)benzenamine.
Yield 89.3~ M.P. 104 106Co Analysis calculated for C15H8F4N4O5 Theory: C, 45.01; H, 2.01; N, 14.00.
Found: C, 45.29; H, 1,95; N, 14.04.
M-(2,6-dinitro-4-hydroxycarbonylphenyl)-4-(1,1,2,2-tetrafluoroethoxy)benzenamine.
Yield 74.6% M.P. 234-236C.
Analysis calculated for C15HllN3O7 Theory: C, 42.97; H, 2~16; N, 10.02.
Found; C, 43.25; H, 2.36; N, 10.10.
N-(2,6-dinitro-3-chloro-4-trifluoromethyl-S phenyl)-4-(1,1,2,2-tetrafluoroethoxy)benzenamine.
Yield 60.3% L~.P. 127-130C.
Analysis calculated ror C15H7ClF7N3O5 Theory: C, 37.70: H, 1.47; ~, 8.80.
Found: C, 37.95; H, 1.53; N, 8.59.
N-(2,4-dinitro-6-hydroxycar~onylphe~yl)-g-(1,1,2,2-tetrafluoroethoxy)benzenamine.
Yield 50.0~ M.P. 192 195C.
An~lysis calculat~d for C15H8F~N3O7 Theory: C, 42.97; H, 2.1~; N, 10.02.
Found: C, 43.23; H, 2.30; N, 9.74.
N-(2,6-dinitro-4 tert.-butylphenyl)-3-(1,1,2,2--tetrafluoroethoxy)benzenamine.
M.P. 12~-131C.
Analysis calculated for C18H17F4N3O5 3G Theory: C, 50.12; H, 3.97; N, 9.74.

Found: C, 50.02i H, 3.89; N, 9.48.

~ ~ f.:~ ~ 3 ~ 9 N-(2,6-dinitro-4-trifluoromethylphenyl)~3-(1,1,2,2-tetrafluoroetho~y)benzenamine. (oil) ~nalysis calculated for C15HgF7N3O5 Theory: C, 40.65; H, 1.82; N, 9.48.
5Found: C, 40.91; H, 1.84i N, 9.24.
N-(2,4-dinitro-6-trifluoromethylphenyl)-3-(1,1,2,2-tetrafluoroethoxy)benzenamine.
M.P. 74-76C.
Analysis calculated for C15H7F7N3O5 10Theory: C, 40.56; H, 1.82; N, 9.48.
Found: C, 40.87; H, 2.02; N, 9.49.
N-(2,6-dinitro-4-trifluoromethylphenyl)-4-(1,1,2,2-tetrafluoroethoxy)benzenaminP.
15Yield 83~5% M.P. 102-105C~
Analysis calculated for C15H8F7N3O5 Theory: C, 40.65; H, 1~82; N, 9.4%.
Found: C, 40.82; H, 1.79; N, 9.63.
N-(2,4,6-trinitrophenyl)-4-(1,1,2,2-tetra-20fluoroethoxy)benzenamine.
M.P. 141-142C.
Analysis calculated for C14H8N4O7 Theory: C, 40.01; H, 1.92; N, 13033.
Found: C, 40.17i H, 2.04i N, 13.09.
25N-(2,4,6-trinitrophenyl~-3-(1,1,2,2-tetra-fluoroethoxy)benzenamine.
M.P. 128-129C.
Analysis calculated for Cl~H8N~O7 Theory: C, 40.01; ~, 1.92; N, 13.33.
Found: C, 40.14; H, 1.99; ~, 13.a4.

3 3 ~3 Example 13 N-(2-trifluoromethyl-4-nitrophenyl)~3-(1,1,2,2-tetrafluoroethoxy)~enzenamine.
Two grams of a 50~ suspension of sodium hydride in mineral oil were washed several times with pentane, and then suspended in 25 ml. of N,N-dimethyl-formamide. To the stirred mixture were added in one portion 3.8 g. of 3-(1,1,2,2-tetrafluoroethoxy)phenyl-amine. The reaction mi~ture was stirred at ambient temperature for thirty minutes, and then 4O5 g. of 2-trifluoromethyl-4-nitrophenylchloride were added dropwise over five minutes to the reaction mixture.
The mixture was stirred for three hours at room tem-perature, and then added slowly to 100 ml. of dilute hydrochloric acid solution. An oil which precipitated was collected, dissolved in diethyl ether, and chroma-tographed over si.lica gel. After collecting the fractions shown by thin layer chromatography to contain a single product and evaporating the solvent therefrom~ there were recovered, as an oil, 2~0 g. of N~(2-trifluorome-thyl-4-nitrophenyl)-3-(1,1,2,2-tetra-fluoroethoxy)benzenamine.
Analysis calculated for C15HgF7N3O3 Theory: C, 45.24; H, 2.2~; N, 7.03.
Found: C, 45.03; H, 2.24; N, 7.09.

1 3 ~ 33~J:

Examples 1~-17 N-(2,6-dinltro~4-trifluoromethylp'nenyl)-2-(1,1~2,2-tetrafluoroethoxy)ben2enamine.
Analy5is calculated for C15H8~7N3O5 5Theory: C, 40.65; H, 1.82, N, 9.480 Found: C, 40.85; H, 1.80; N, 9.48.
N-~2,4-dinitro-6-hydroxycar~onylphenyl)-2-(1,1/2,2-tetrafluorcethoxy)benzenamlne.
10Analysis calculated for C15HgF4N3O7 Theory: C, 43.08; H, 1.93; N, 10.05.
Found: C, 43.27; H, 2.01; N, 9.81.
N-(2,4,6-trinitrophenyl)-2-(1,1,2,2-tetra-fluoroethoxy~benzenamine.
15M.P~ 114-115C.
Analysis calculated for C14H8FaN4O7 Theory: C, 40.01; H, 1.32; N, 13.33.
Found: C, 39.88, H, 1.99; N, 13.62.
N-(2,4-dinitro-6-tert.-butylphenyl)-4~
(1,1,2,2-tetrafluoroethoxy~benzenamine.
M.P. 98-101C.
Analysis calculated or C18H17F4N3O5 Theory: C, 50.12; H, 3.97; N, 9.74.
25Found: C, 50.24; ~, 4.01; N, 9.86.
Example 18 N-(2,4-dinitro-6-trifluoromethylphenyl)-N-methyl-3-(1,1,2,2-tetrafluoroethoxy)~enzenamine.
A solution of 4.0 ml. of dimethylsulfate 30in 30 ml. of acetone containing 5.0 g. of sodium 3 ~ 9 carbonate and 3.0 g. of N-(2,4-dinitro-6-trifluoro-methylphenyl)-3-(1,1,2,2-tetrafluoroethoxy)benzen-amine was heat~d at reflux for sixteen hours. An additional 2.0 ml. of dimethyl sulfate was added to

5 the reaction mixture, and refluxing was continued for an additional four hours. The reaction mixture was cooled to room temperature and diluted by the addition of 150 ml. of water. The aqueous mixture was stirred for thirty minutes, and then the product was extracted into diethyl ether. The ethereal extracts were combined, washed with water, dried, and the solvent was removed by evaporation under reduced pressure to provide 3.7 g. of an oil, identified as N-(2,4-dinitro-6-trifluoromethylphenyl)-N-methyl-3-~1,1,2,2-tetxafluoroethoxy)~enzenamine.
Analysis calculated for C16H7F7N3O5 Theory: C, 42.03; H, 2.20; N, 9.19.
Found: C, 42.24; H, 2.34; ~, 9.320 Example 19 ~0 Following the proc dure of Example 13, N-(2,4-dinitxo-6-trifluoromethylphenyl)-4-(1,1,2,2-tetrafluoroethoxy)~enzenamine was reacted with dimethyl sulfate and sodium carbonate in acetone to provide N-(2,4-dinitro-6-trifluoromethylphenyl)-N-methyl-4-(1,1,2,2-tetrafluoroethoxy~benzenamine.
M.P. 91-92C.
Analysis calculat~d for C16H7F7M3O5 Theory: C, 42.03; H, 2.20; N, 9.19.
0 Found: C, 42.27; H, 2.06; N, 9.43.

Example 20 N-~2,4-dinitro-6-trifluoromethylphenyl)-N-methyl-2,4-di~romo-5-(1,1,2,2-tetrafluoroethoxy)-benzenamine.
To a stirred solution of 1.5 g. of N-(2,4-dinitro-6-trifluoromethylphenyl)-N-methyl-3-tl,l,2 r 2-tetrafluoroethoxy)benzenamins in 30 ml. of acetic acid containing 10 ml. of water were added in one portion 1.5 mlu of bromine. The reaction mi~ture was stirred for three hours at room temperature, and then was diluted by the addition of 30 ml. of water.
The mixture was stirred for an additional one hour, and then the solvent was decanted to leave a solid precipitate. The solid was dissolved in diethyl ether, li dried, and the solvent was removed by evaporation under reduced pressure to afford 1.8 g. of N-(2,4-dinitro-

6-trifluoromethylphenyl~-N-methyl-2,4-dibromo-5-(1,1,2,2-tetrafluoroethoxy)benzenamine.
M.P. 97-99C
An~lysis calculated for C16H8Br2F7N3O5 Theory: C, 31.25; H, 1.31; N, 6.83.
Found: C, 31.26; H, 1.38; N, 6.92 Examples 21-22 Following the procedure of Example 20, a halogen was reacted with a benzenamine to give the following halogenated benzenamines:
N-~2,4-dinitro-6 trifluoromethylphenyl)-2,6-dichloxo-4-(1,1,2,2-tetr~1uoroethoxy)ben2en-amine.
.

~ ~ 6~.~3~

M.P. 80 82C.
Analysis calculated for C15H6C12F7N3O5 Theory: C, 35.18; H, 1.18; N, 8.210 Found: C, 35.48; H, 1.31; N, 8~50.
5N-(2,4-dinitro-6-trifluoromethylphenyl)-2,6-di~romo-4-~1,1,2 r 2-tetrafluoroethoxy)benzenamine.
M.P. 92-93QC.
Analysis calculated for C15H6Br2F7N3O5 Theory: C, 29.98; H, 1.01; N, 6.99.
10Found: C, 30.12; H, 1.05; M, 3.17.
Example 23 N-~2,4,6-trinitrophenyl)-2,4-dibromo-5-(1,1,2,2-tetrafluoroethoxy)benzenamine.
15To a stirred solution of 1.7 g. of N-(2,4,6-trinitrophenyl)-3-(1,1,2,2-tetrafluoroetho-xy)-benzenamine in 20 ml~ of dichloromethane were added in one portion of 1.5 ml. of bromine. The reaction mix-ture was heated at reflux for sixteen hours, and then 1.0 ml~ of bromine was added. The mixture was reflu~ed for an additional two hours, and then cooledto room temperature. The precipitate which formed was collected by filtration to provide 1.4 g. of N-(2,4,6-trinitxophenyl~-2,4-dibromo-5-~1,1,2,2-~e~rafluoro-ethoxylbenzenamine.
MoP~ 201-203C.
~nalysis calculated for C14H5Br2F4N4~7 Theory: C, 29009; H, 1.05; N, 9.69.
Found: C, 29.35; H, 0.96; N, 9.~1.

~ 1 ~433g Exarnples 24-26 Varlous benzenamines were halogenated in dichloromethane by the procedure of Example 23 to give the following halo subs~ituted benzenamines:
~ ,6-dinitro~4-trifluoromethylphenyl)-2,4-dichloro-5-(1,1,2,2-tetrafluoroethoxy)benzenamine.
M.P. 142-143C.
Analysis calculated for C15H6Cl~F7~3~5 Theory: C, 35,18; H, 1.18; N, 8.21.
Found: C, 35.48; H, 1.19; N, 8.12.
N-~2,6-dinitro-4-trifluoromethylphenyl)-2,4-dibromo-5-(1,1,2,2-tetrafluoroethoxy)benzenamine.
M.P. 161-163C.
Analysis calculated for C15H6Br2F7N3O6 Theory: C, 29.98; H, 1.01; N, 6.99.
Found: C, 30.04; ~, 1.1~; N, 7.14.
N-(2,4-dinitro-6 trifluorometh~lphenyl)-2,4-dibromo-5-(1,1,2,2-tetrafluoroethoxy)benzen-amine. (oil~
Analy5is calculated for C15H6Br~F7N3O5 Theory: C, 36.94; H, 1.77; N, 9.24.
Found: C, 37.~4; H, 2.05; N, 9.55.

As hereinbefore pointed out, the c~mpounds of this invention have several utilities, including plant and soil antifungicidal activity. In a further embodi-ment of this invention, there are provided formulations for use in treating plant and soil fungicidal infections.
Such formulations comprise a benzenamine of the above formula admixed with a suitable carrier, diluent or excipient therefor.

As used herein, the term "carrier", "diluent"or "excipient" refers to a ~aterial or materials with formulated to facilitate its storage, transport, hardllng, and administration to animals or application to plants or soil. Such carriers, diluents and excip-ients can be solid or liquid, and are preferably substantially inert chemically and biologically.
Commonly used solid carriers for use in dust formu-lations include gypsum, tripolite, diatomaceous earth, mineral silicates, vermiculite, talc, clays, calcium and magnesium limes, calcite and related can be employed if desired. Typical liquid carriers include water, saline, or organic fluids such as oils, for example a horticultural petroleum product.
1~ The formulations comprehended by this ln-vention comprise a suitable carrier, diluent or exclp-iant admixed with a ben2enamine of the abo~e formula.
The formulations will contain from about 5 to about 90 percent by weight of a benzenamine provided by this invention. A preferred concentr~tion of acti~e in-gredient is from about 20 to about 80 percent by weiyht. The combination can take the form of con-centrates, for instance aqueous emulsions or the like, or as spraysl dry powders, wettable powders, and the like. Preferred formulations include wettable powders, which are solid compositions of matter wherein the benzenamine is absorbed or absorbed in or on a ~orptive carrier such as finely divided clay, talc, gypsum, lime, wood flour, kieserl~uhr or the like. ~,~ett~ble powder formulations commonly contain a small amourlt o . 3 3 g X-~836-1 -24-a wetting, dispersing or emulslfying a~ent to facilitate dispersion in water or other liquid carriers utilized to distribute the active ingredient to the locus of desired fungus control. Commonly used wetting ayents include condensed aryl sulfonic acids and sodium salts thereof, alkyl aryl polyether alcohols, sulfonated nonionic blends, anionic wetting agents, and the like.
Other preferred formulations according to this invention are emulsifiable concentrates, which are homogenous liquid or paste compositions of benzenamines ~hich readily disperse in water or other liquid carrier to make a liquid which facilitates application to the locus of desired fungus control. Typical emulsifiable concentrates will contain a benæenamine of the above-formula admixed with an organic solvent such as xylene,heavy aromatic naphthas, dioxane, or dimethylformamide, in addition to one or more emulsifying agents such as phenols, polyoxyethylene derivatives of sorbitan esters~, complex ether-alcohols, and the like. Other ingredients such as antifreezes, antifoaming agents, stabilizers, antibacterial agents and the like can be utilized if desired.
E~ample 27 and 28 which follow illus~rate typical formulations contemplated herein.

1 ~ 6~339 ExamPle ?7 Wettable Powder Formulation Ingredient Percent by Weight . . .
N-(2-~rifluoromethyl-5-chloro-4,6-dinitrophenyl)-4-(1,1,2,2-tetraflu~ro-ethoxy)~enzenamine 25.8 Stepano~ ME) 5.0 Polyfo~ ) Wetting and 5.0 Zeole~7 ) dissipating agents 10.0 Bardens Clay 54O2 The above ingredients are mixed and air milled to provide a finely divided uniform powder. The powder is dispersed in water at the site of application and sprayed on the locus where fungal control is desired. The rate of application is about 5 to about 30 pound~ of active ingredient per acre.
Example 28 _ Emulsifiable Concentrate Formulation IngredlentPerce t by Weisht N-(2,6~dinitro-~-trifluoro-methylphenyl~-2,4-dichloro-: 5-(1,1,2,2-tetrafluoro-ethoxy)benzenamine~3.5 Orthochlorotoluene 18.5 Ethoxylated polyoxypropylene glycol surfactant t~t1O ~
~916TF) 5 0 Propylene glycol 1.0 Water 33.0 , -~ 1 6~39 The above ingredients are combined -to form an aqueous emulsion which is to be diluted by additional water at the site of application. Such diluted formulation will be applied to the soil to be treated at a rate such 5 that the active ingredient is about 10 to about 20 pounds per acre.
The compounds provided by this invention ha~e several utilities, including ectoparasitic activity, insecticidal acti~ity, as well as antifungal activity.
A further embodiment of this invention is a method for treating and controlling fungal diseases in soil and on growing plants. The benzenamines defined by the above general formula can be applied as a drench to soil and incorporated therein prior to the emergence of plant seedlings, or can alternatively be applied to the foilage o~ growiny plants such as cotton, beans, in-cluding soybeans and the like. The compounds are effective against a number of plant pathogenic fungi when applied per- or post-emergent at rates of about 20 Ool to about S0 pounds per acre, ideally about 10 to about 20 pounds per acre. The compounds are effective in controlling and treating several common fungal diseases, including those caused by pathogens of the species Rhizoctonia, Fusarium (root rot), Verticillum (wilt), Pythium and the like.
A number of the compounds provided herein have been evaluated as antifungal agents in standard greenhouse tests. In a typical test, a bPnzenamine cf this invention was formulated by mixing 70 mg. of the compound with 2 ml. of a solution comprising 500 ml. of '1 3 3 9 X-4836-l 27-ethanol, 500 ml. of acetone, and 100 ml. of Tween 20 (a polyoxyethylene sorbitan monolaurate made by Atlas Che~ical Division of ICI America, Inc., ~lilmington, Delaware). The mixture thus formed was diluted ~ith 175 ml. of deionized water containing one drop of antifoam C emulsion per 2 liters of water. The final formulation contain~d 400 ppm. of benzen~mine test compound, 10,000 ppm~ of organic solvents~ and 1,000 ppm. of Tween 20. This solution was diluted with deionized water to obtain desired lower concentrations of active ingredient.
On the day a test was initiated, young ex-panding leaves of plants were detached and placed bottom side up in petri dishes containing filter paper placed on top of an expanding plastic mat to keep the lea~es above the water flooding tne bottom of the dishes. A water-soaked wad of cotton was wrapped around the petriole base of the leaf. The test chemical at the desired concentration was sprayed on the under side of the leaves to run off and the leaves were then allowed to dry. The dried leaves inoculated by spraying with a suspension of pathogenic fungi using a DeVilbiss s~rayer. After inoculation, the dishes were placed in a moist chamber. The leaves were observed for disease symptoms anZ the results were recorded seven da~s ar~er treatment. A rating scale of 1 to 5 was used to record the results, i~. which scale "1" equals severe disease, "2" equals moderately severe disease, "3" e~uals moderate disease, "4" eauals slight disease and "5"
equals no disease.

'113 1 3 3 ~

The results of such test ls presented in Table I which follows. Column A in the table identifies the benzenamine evaluated. Column B gives the appli-cation rate in parts per milli.on (pp~). Column C li~ts the rating of control against each of the indicated species of fungal infection.

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i 3 64339 ( Compounds o~ this invention have additionally been evaluated in soil disease tests to demonstrate their antifungal activity. Test compounds were ~ormu-lated by dissolving 57 mg. of compound in l ml. of a fifty percent (VJV) solution of acetone and ethanol. A
O.l~ aqueous solution of Tween 20 was added to bring the final volume to 16 ml.
Pathogen-infested soil was placed in 8 o~.
paper cups~ A depression wa~ made in the surface of the soil and 3 g. of Celator~lP-78 granules were ~laced in the depression. A 4 ml. aliquot of chemical formu-lation was added to the granules, and the cups were then covered with lids. The containers are shaken ky hand for about lO seconds, and then placed on a roller lS fcr about 10 minutes to thoroughly incorporate the test chemical into the soil. The treated soil was trar.sferred to a 2.5 inch round plastic pot, and seeds of the hGst plant w~re added, and cov2red with additicnal treate~
soil. The effect of the test compounds was observed on the growing plants and was rated on a scale of l to 5 (1 is severe dlsease, S is no disease). The results of such evaluations are preserted in Table II. Colu~n A
lists the co~pounds evaluated. Column 3 lists the application rates in pounds per acre (lbs/ac). Column C reco as the plant variety. Colu~n D lists the pathogen and the disease rating for the tested ccm~ound.

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The data thus presented in Tables I and II
demonstrate that the compounds of this invention can be used to control or treat diseases occuring in soil and plants and caused by pathogenic fungi. A further S embodiment of this invention accordingly i5 an anti-fungal method which comprising applying to the locus to be treated an antifungal a~ount of a benzenamine of this invention. As already noted, the compounds can be formulated in any of a number of ways to facilitate convenient application to soil or to growing plants.
The compounds are preferably applied as a liquid spray or drench, or alternatively as a dust or granule.
While the specific rate of application of benzenamine may vary depending upon the disease to be treated, the host plant, the soil conditions of moisture and texture, the typical rate of application for field use will be about 0.1 to about 50 pounds per acre, and more pref-erably about 10 to about 20 pounds per acre.
The benzenamines of this invention have also demonstrated good ectoparasitic activity. For example, N-(2,4-dinitro-6-trifluoromethylphenyl)-3-(1,1,2,2-tetrafluoroethoxy)benzenamine demonstrated complete control of adult housefly and blowfly larva in standard tests designed to show ectoparasitic ac-tivity. Com-pounds such as N-(2,4-dinitro-3-chloro-6-trifluoro-methylphenyl)-4-~1,1,2,2-tetraflucroethory)benzenamine and N-(2,4-dinitro-3~bromo-6-trifluoro~ethylphenyl)-4-~1,1,2,2,2-pentafluoroethoxy)benzenamine are con-templated as excellent insecticidal agents.

Claims

X-4836-Canada -35-The embodiments of the invention for which an exclusive property or privilege is claimed are defined as follows:

1. A formulation useful in the treatment of fungal infections in soil and on plants comprising an antifungal amount of a compound of the formula wherein:
RO is hydrogen or fluoro;
R1 is hydrogen or C1-C2 alkyl;
R2 and R independently are hydrogen or halo;
R4 is hydrogen, trifluoromethyl, cyano, C1-C4 alkyl, hydroxycarbonyl or C1-C4 alkoxycarbonyl;
R5 is hydrogen, halo, nitro, hydroxy, methoxy or amino;
R6 is hydrogen or nitro; and the physio-logically-acceptable salts thereof, and a suitable carrier therefor.

2. The formulation of Claim 1 wherein the active ingredient has the formula X-4836-Canada -36-wherein:
R0 is hydrogen or fluoro;
R1 is hydrogen or C1-C2 alkyl;
R2 and R3 independently are hydrogen or halo;
R5 is hydrogen or halo; and the physio-logically-acceptable salts thereof

3. The formulation of Claim 1 wherein the active ingredient is N-(2,4-dinitro-6-trifluoro-methylphenyl)-2,4-dibromo-5-(1,1,2,2-tetrafluoro-ethoxy)benzenamine.

4. The formulation of Claim 1 wherein the active ingredient is N-(2,6-dinitro-4-trifluoromethyl-phenyl)-2,4-dichloro-5-(1,1,2,2-tetrafluoroethoxy)))-benzenamine.

5. The formulation of Claim l wherein the active ingredient is N-(2,4-dinitro-6-trifluoromethyl-phenyl)-3-(1,1,2,2-tetrafluoroethoxy)benzenamine.

6. The formulation of Claim 1 wherein the active ingredient is N-(2-trifluoromethyl-4-nitro-phenyl)-3-(1,1,2,2-tetrafluoroethoxy)benzenamine.

7. A method for the treatment of plant and soil fungal infections which comprises applying to the locus to be treayed an antifungal amount of a compound of the formula X-4836-Canada -37-wherein:
R0 is hydrogen or fluoro;
R1 is hydrogen or C1-C2 alkyl;
R2 and R3 independently are hydrogen or halo;
R4 is hydrogen, trifluoromethyl, cyano, C1-C4 alkyl, hydroxycarbonyl or C1-C4 alkoxycarbonyl;
R5 is hydrogen, halo, nitro, hydroxy, methoxy or amino;
R6 is hydrogen or nitro; and the physio-logically-acceptable salts thereof.

8. The method of Claim 7 wherein the active compound applied is wherein:
R0 is hydrogen or fluoro;
R1 is hydrogen or C1-C2 alkyl;
R2 and R independently are hydrogen or halo;
R5 is hydrogen or halo; and the physiologically-acceptable salts thereof.

9. The method of Claim 7 wherein the active compound applied is N-(2,4-dinitro-6-trifluoromethyl-phenyl)-2,4-dibromo-5-(1,1,2,2-tetrafluoroethoxy)-benzenamine.

X-4836-Canada -38-

10. The method of Claim 7 wherein the active compound applied is N-(2,6-dinitro-4-trifluoromethyl-phenyl)-2,4-dichloro-5-(1,1,2,2-tetrafluoroethoxy))-benzenamine.

11. The method of Claim 7 wherein the active compound applied is N-(2,4-dinitro-6-trifluoromethyl-phenyl)-3-(1,1,2,2-tetrafluoroethoxy)benzenamine.

12. The method of Claim 7 wherein the active compound applied is N-(2-trifluoromethyl-4-nitrophenyl)-3-(1,1,2,2-tetrafluoroethoxy)benzenamine.